CN1043535A - Sulfuric acid pickling waste liquid regenerated processing method - Google Patents
Sulfuric acid pickling waste liquid regenerated processing method Download PDFInfo
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- CN1043535A CN1043535A CN 88108685 CN88108685A CN1043535A CN 1043535 A CN1043535 A CN 1043535A CN 88108685 CN88108685 CN 88108685 CN 88108685 A CN88108685 A CN 88108685A CN 1043535 A CN1043535 A CN 1043535A
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- sulfuric acid
- waste liquid
- pickling waste
- ferrous sulfate
- acid pickling
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
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Abstract
Processing method of the present invention relates to and contains sulfuric acid, the regeneration of the spent pickle liquor of ferrous sulfate, this processing method is to add the vitriol oil in the spent pickle liquor that is higher than room temperature, the amount that adds the vitriol oil makes that vitriolic concentration is 20-30% (weight percentage) in the spent pickle liquor, and the ferrous sulfate crystallization is separated with sulphuric acid soln.This processing method is reclaim(ed) sulfuric acid and ferrous sulfate simultaneously, does not discharge the three wastes, and is free from environmental pollution, and technology, equipment are simple, consumes energy not, and cost is low, has remarkable economic efficiency.
Description
Processing method of the present invention relates to the regeneration of sulfuric acid pickling waste liquid, contains the regeneration of ferrous sulfate, vitriolic spent pickle liquor more precisely.
In industrial production,, or, often need to carry out surface derusting, pickling process is all arranged as job shops such as the steel rolling of steel mill, forging, steel wire, steel pipes to before the reprocessing of its goods to the steel product first being processed.The indispensable especially link of the pickling process of Electroplate Factory.But in pickling process, produce a large amount of spent acid.
The method of surface derusting has two big classes, and the one, with the method for mechanical rust removals such as sandblast, spark-out; The 2nd, adopt the chemical method rust cleaning, i.e. the acid pickling and rust removing method.Acid pickling and rust removing generally is to adopt sulfuric acid or aqueous hydrochloric acid to carry out.Because sulfuric acid has inexpensive and advantage non-volatility, adopts the vitriolic aqueous solution as pickle solution more.
In acid cleaning process, adopt the 20-30%(weight percentage more) aqueous sulfuric acid carries out down together, generates ferrous sulfate (FeSO along with the reaction of sulfuric acid and iron rust and iron
4) and consumed the sulfuric acid in the pickle solution, the sulfuric acid concentration in the pickle solution is reduced.Vitriolic concentration is reduced to 5-7% in pickle solution, and the content of ferrous sulfate has just become sulfuric acid pickling waste liquid when 24-26%, can only discharge as waste liquid.This waste liquid causes the pollution to environment, so must be handled this waste liquid if do not emit with not adding processing.
Current, the method for handling this waste liquid has three kinds: first kind is with alkali, lime neutralization sulfuric acid wherein, makes PH in the waste liquid reach 6-9 and emits.The shortcoming that this treatment process exists is to cause potential to pollute, and also will consume a large amount of alkali, chemical materialss such as lime, and also the sulfuric acid in the waste liquid and ferrous sulfate can not get reclaiming, and slattern in vain.If adopt the lime neutralization, generate a large amount of calcium sulfate and bring difficulty to discharging.Second method is to add iron filings and the reaction of spent acid wherein in this vitriolated waste liquid, carries out evaporation concentration and generates the ferrous sulfate crystallization.This method has been compared many advantages with first method, eliminated the potential pollution, need not consume chemical materialss such as a large amount of alkali or lime, and can reclaim the Chemicals ferrous sulfate, its shortcoming is to consume a large amount of iron filings, can not reclaim more valuable industrial chemicals sulfuric acid again, and make the unnecessary sulfuric acid in the waste liquid become ferrous sulfate, and evaporation concentration need consume a large amount of energy.The third method is with waste liquid graphite evaporator evaporation concentration, and the ferrous sulfate crystallization is separated with sulfuric acid, and 85% the sulfuric acid that obtains returns, and is used to prepare new pickle solution.This method has more advantage than the first two kind method, not only can reclaim the Chemicals ferrous sulfate, and the Chemicals sulfuric acid of recyclable preciousness does not consume various chemical materialss such as iron filings, alkali, lime again again.The shortcoming of this method is to need special corrosion resistant evaporation equipments, also will consume a large amount of energy, moreover exists a large amount of thin crystalline particles in the ferrous sulfate crystallization that obtains of this method, wears filter during filtration easily, operation inconvenience.
American documentation literature US 3,743,484 has introduced the useless vitriolic processing method of a kind of recovery, this method is that sulfuric acid pickling waste liquid and crystallization are gone out recycle sulfuric acid (sulfuric acid concentration 40-50% behind the ferrous sulfate, weight percentage, down together), in tempering tank, mix the mix sulphur acid solution.The mix sulphur acid solution is imported in the heating vacuum vaporation device, and heating concentrates said mix sulphur acid solution in the heating vacuum vaporation device, obtains containing sulfuric acid and the 10-30% ferrous sulfate crystalline aqueous slurry of 40-55%.Ferrous sulfate is separated with sulfuric acid.The cyclic part of the sulfuric acid (recycle sulfuric acid) that reclaims is mixed with sulfuric acid pickling waste liquid.The advantage of this method is that most ferrous sulfate crystallization is a coarse particles, is convenient to filter.Sulfuric acid obtains recycle, and is again can reclaim(ed) sulfuric acid ferrous.Its shortcoming is still to need equipment such as special corrosion resistant heating vacuum vaporation device, water cooler, crystallizer, also will consume a large amount of energy.
Purpose of the present invention just is to overcome the shortcoming of above-mentioned several processing methodes, it is simple to work out a technology, be convenient to the operating equipment less investment, without concentration and evaporation, consumes energy not, can reclaim(ed) sulfuric acid ferrous, the processing method that can make the sulfuric acid in the sulfuric acid pickling waste liquid obtain reclaiming be utilized whole sulfuric acid pickling waste liquids completely again.
Processing method of the present invention is in being higher than the sulfuric acid pickling waste liquid of room temperature, adding the vitriol oil mixes, the amount of the vitriol oil that is added, making the sulfuric acid concentration in the sulfuric acid pickling waste liquid is the 20-30%(weight percentage) naturally cool to room temperature again, the ferrous sulfate crystallization is separated out, the ferrous sulfate crystallization is separated with sulphuric acid soln, and isolated sulphuric acid soln is as the regenerated sulfuric acid pickling solution.
Because iron rust, iron and the sulfuric acid reaction of ironware, steel piece surface is thermopositive reaction in acid cleaning process, can make the temperature of sulfuric acid pickling solution be elevated to 45 °-49.9 ℃, so in 45 °-49.9 ℃ sulfuric acid pickling waste liquid, add the vitriol oil for well, need not heat in addition like this, saved the energy.Owing to contain 20-30%, the sulfuric acid degree of ionization height of (weight percentage) is 20-30% so the vitriolic pickle solution generally is made into vitriolated concentration.Therefore add the amount of the vitriol oil in sulfuric acid pickling waste liquid, making the vitriolic concentration in the sulfuric acid pickling waste liquid is 20-30%.Isolate like this after the ferrous sulfate crystallization, can add sulfuric acid no longer in addition,, directly apply to pickling directly as new pickle solution.Certainly can also add the vitriol oil and make sulfuric acid concentration in the sulfuric acid pickling waste liquid more than 30%, but the regenerated pickle solution will add relatively large water dilution, it is not quite convenient to operate.Add sulfuric acid on the contrary less, must add sulfuric acid again after then isolating ferrous sulfate, and the ferrous sulfate eduction rate is low.
After the pickle solution of sulfur acid 20-30% was used for pickling, when vitriolic concentration was reduced to 5-7% in the pickle solution, speed of response reduced, and in order to guarantee to eliminate rust better, should change pickle solution.Therefore general vitriolated concentration is 5-7% in the sulfuric acid pickling waste liquid, the ferrous 24-26% of sulfur acid.For example contain the new pickle solution of 25% vitriolic, when this pickle solution sulfuric acid concentration reduces to 6%, consumed 72.8% sulfuric acid, at this moment sulfur acid ferrous 24.9%.
After adding the vitriol oil make its vitriolic concentration reach 20-30% in containing the vitriolic spent pickle liquor, naturally cool to room temperature, do not need artificial refrigeration, consumes energy not also can reduce chilling unit like this.Whether the season of said room temperature and various places, geographical position have heating installation relevant, and generally between 15 ℃-25 ℃, certainly, the temperature of room temperature is low more good more for room temperature usually, and the temperature of room temperature is low more, and the rate of recovery of ferrous sulfate will increase.For example contain 6% sulfuric acid, 24.9%(weight percentage, down with) sulfuric acid pickling waste liquid of ferrous sulfate in the time of 40 ℃, do not separate out the ferrous sulfate crystallization.When temperature is reduced to 30 ℃, only there is 4% ferrous sulfate to separate out.Test shows the regenerated pickle solution that contains ferrous sulfate, does not influence the pickling of ironware, steel part.
Isolating vitriolic concentration behind the ferrous sulfate for control better can add water (distilled water, ion exchanged water all can) or add the vitriol oil and be mixed with required sulfuric acid concentration more accurately.
Separate useable glass cloth, filter paper filtering with the ferrous sulfate crystalline in order to carry out sulfuric acid.In order to improve the quality of byproduct ferrous sulfate, being good with the whizzer centrifugation.
Advantage of the present invention just is:
[1] eliminated the heating evaporation enrichment process, just can reclaim and obtain technical grade ferrous sulfate (green vitriol) byproduct, again can reclaim(ed) sulfuric acid.This technology utilization the reaction heat of sulfuric acid and iron rust, iron, and naturally cool to room temperature.Saved the energy, made the sulfuric acid pickling waste liquid can closed cycle again, sulfuric acid is fully used, no waste discharge in the technological process, free from environmental pollution.
[2] this processing method technology is simple, and the ferrous sulfate crystal of generation is a coarse crystal, is easy to filtration, is convenient to operate, only need be with simple devices such as acidproof crystallizer tank, water pot, acid jar, acid proof pumps with regard to the energy suitability for industrialized production, and less investment, cost is low.
[3] this technology three-waste free discharge not only, and remarkable economic efficiency arranged, make in the present pickling vitriolic utilization ratio from 70-75%, bring up to 100%, in 1000 tons of vitriol oils of acid pickling and rust removing consumption, can obtain 2800 tons in ferrous sulfate every year, reclaim 250-300 ton sulfuric acid simultaneously, 500,000 yuan of worth up tos.The net earnings of this technology is 1.3 times of evaporation concentration method, is 2.1 times of adding iron filings neutralisation.
Handle sulfuric acid pickling waste liquid operation technological process figure as shown in Figure 1:
By pickling tank [1], by acid proof pump [2] sulfuric acid pickling waste liquid is transported in the crystallizer tank [3], the vitriol oil that in crystallizer tank, adds requirement by high-order sulfuric acid tank [6], mix with sulfuric acid pickling waste liquid, crystallization goes out ferrous sulfate, and separate, the regenerated sulfuric acid lotion is transported in the pickling tank [1].In pickling tank [1], add entry or acid by water pot [4] or acid jar [5], make pickle solution align needed sulfuric acid concentration.
More specifically describe the present invention with following non-limiting examples, protection scope of the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
The vitriol oil and 110 ml distilled waters of getting 7.6 milliliter 98% are made into dilution heat of sulfuric acid in beaker, add 102 gram FeSO
47H O is heated to 49.9 ℃, makes its dissolving, stirs, and this moment, the composition of mixing solutions was:
H
2SO
4: the 6.06%(weight percentage, down together)
FeSO
4：24.68%
H
2O：69.26%
The gross weight of this mixing solutions is 226 grams, its composition be equivalent to end composition of sulfuric acid pickling waste liquid.19.6 milliliters of the vitriol oils of adding 98% in above-mentioned mixing solutions, static placement is spent the night (placing about about 15 hours), makes its temperature drop to 21 ℃ naturally, separates out FeSO
47H2O uses filter paper filtering, and elimination solution gets green vitriol 78.5 grams, adds 16.1 milliliters of distilled water in filtrate, and it consists of (weight percentage, down together) to obtain the regenerated pickle solution
H
2SO
4：25%
FeSO
4：6.4%
The gross weight of regenerating acid washing lotion is 200 grams, and this liquid is returned as new pickle solution, is used for pickling, FeSO
47H
2The eduction rate of O is 77%, by four repeated experiments, and the data basically identical of gained.
Embodiment 2
Get sulfuric acid pickling waste liquid in the factory, its composition is as shown in table 1.
The percentage composition (weight percentage) that above-mentioned sulfuric acid pickling waste liquid is converted into each component is:
H
2SO
4：6.8%
FeSO
4：26.3%
Fe
2（SO
4）
3：0.15%
Get 500 milliliters of 49.9 ℃ of sulfuric acid pickling waste liquids of above-mentioned factory, add 60 milliliter 98% the vitriol oil, after stirring, static placement is spent the night (about about 14 hours), makes its temperature reduce to 20 ℃ naturally, and lot of F eSO is arranged
47H
2O separates out, and leaches solution with filter paper, gets green vitriol crystal 2 51 grams.
Consisting of of filtrate:
H
2SO
4：30.2%，
FeSO
4：5.5%。The density of filtrate is 1.23, and after filtrate added distilled water, making its vitriolic concentration was 30%.The eduction rate of ferrous sulfate is 80.2%, and the vitriolic utilization ratio is 100%.The vitriolic additional amount is 71.3%, and promptly the vitriolic reclamation rate is 28.7%.
The FeSO that separates out
47H
2Being analyzed as follows of O product:
Substances content %
Ferrous sulfate＞99.00 with 7 crystal water
Water-insoluble＜0.02
Muriate＜0.005
Calcium＜0.01
Manganese＜0.02
Arsenic＜0.00005
Alkalies and alkaline earth (in vitriol)＜0.2
Claims (3)
1, a kind of sulfuric acid pickling waste liquid regenerated processing method, in sulfuric acid pickling waste liquid, adding the vitriol oil mixes, feature of the present invention is, the temperature of sulfuric acid pickling waste liquid is higher than room temperature, it is 20-30% (weight percentage) that the amount of the adding vitriol oil makes the sulfuric acid concentration in the sulfuric acid pickling waste liquid, naturally cools to room temperature, and the ferrous sulfate crystallization is separated with sulphuric acid soln.
According to a kind of sulfuric acid pickling waste liquid regenerated processing method of claim 1, it is characterized in that 2, the temperature of sulfuric acid pickling waste liquid is 45 °-49.9 ℃.
3, according to a kind of sulfuric acid pickling waste liquid regenerated processing method of claim 1, it is characterized in that vitriolic concentration is 5-7% in the sulfuric acid pickling waste liquid, the ferrous 24-26% of sulfur acid in the sulfuric acid pickling waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108685 CN1043535A (en) | 1988-12-24 | 1988-12-24 | Sulfuric acid pickling waste liquid regenerated processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108685 CN1043535A (en) | 1988-12-24 | 1988-12-24 | Sulfuric acid pickling waste liquid regenerated processing method |
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| Publication Number | Publication Date |
|---|---|
| CN1043535A true CN1043535A (en) | 1990-07-04 |
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|---|---|---|---|
| CN 88108685 Pending CN1043535A (en) | 1988-12-24 | 1988-12-24 | Sulfuric acid pickling waste liquid regenerated processing method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061104C (en) * | 1995-02-15 | 2001-01-24 | 安德里茨-专利管理有限公司 | Process for regeneration of electrolytes, in particular of Na2SO4 from waste pickles for stainless steel, in particular, stainless steel strips |
| CN105600836A (en) * | 2016-01-25 | 2016-05-25 | 化工部长沙设计研究院 | Method for recycling useful ingredients in acid pickling waste liquid |
| CN106282577A (en) * | 2016-08-31 | 2017-01-04 | 重庆大学 | The recycling of a kind of stainless steel acid cleaning waste water and processing method |
| CN111803995A (en) * | 2020-07-31 | 2020-10-23 | 北京神州瑞霖环境技术研究院有限公司 | Natural evaporation crystallization system for acid bath discharge liquid reflux removal part and application |
-
1988
- 1988-12-24 CN CN 88108685 patent/CN1043535A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061104C (en) * | 1995-02-15 | 2001-01-24 | 安德里茨-专利管理有限公司 | Process for regeneration of electrolytes, in particular of Na2SO4 from waste pickles for stainless steel, in particular, stainless steel strips |
| CN105600836A (en) * | 2016-01-25 | 2016-05-25 | 化工部长沙设计研究院 | Method for recycling useful ingredients in acid pickling waste liquid |
| CN106282577A (en) * | 2016-08-31 | 2017-01-04 | 重庆大学 | The recycling of a kind of stainless steel acid cleaning waste water and processing method |
| CN106282577B (en) * | 2016-08-31 | 2018-01-05 | 重庆大学 | The recycling and processing method of a kind of stainless steel acid cleaning waste water |
| CN111803995A (en) * | 2020-07-31 | 2020-10-23 | 北京神州瑞霖环境技术研究院有限公司 | Natural evaporation crystallization system for acid bath discharge liquid reflux removal part and application |
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